The construction of an S-scheme heterojunction can facilitate the separation and utilization of photogenerated charges, as well as reserve the reducing power of electrons to induce proton reduction for H2 evolution. In this study, CuCo2S4 nanoparticles and ZnIn2S4 nanoflowers were both synthesized via a hydrothermal method, and then CuCo2S4 was employed to decorate ZnIn2S4 to form CuCo2S4/ZnIn2S4 heterojunction through a simple physical solvent evaporation strategy. The experiment result shows that the rate of photocatalytic H2 evolution (rH2) over 10 wt.% CuCo2S4/ZnIn2S4 can reach up to 20421.3 μmol·g-1·h-1, which is 4.0 times that of ZnIn2S4 (5062.5 μmol·g-1·h-1) and 144.6 times that of CuCo2S4 (141.2 μmol·g-1·h-1). The improved activity results from the establishment of an S-scheme charge transfer way between CuCo2S4 and ZnIn2S4, which facilitates efficient charge separation while preserving active e- and h+. Besides, the formation of the heterojunction broadens the range of light absorption, promotes charge carrier generation, reduces charge transfer impedance, and increases electrochemically active surface area, these together lead to faster H2 evolution kinetics. The present study demonstrates the potential of bimetallic sulfides as a promising catalyst for construction ZnIn2S4-based photocatalysts for efficient solar conversion.